Magnetic recording medium

ABSTRACT

A magnetic recording medium is formed from a non-magnetic support, and a magnetic layer formed on the support and including mainly a binder resin and a ferromagnetic metal powder including mainly Fe. The magnetic layer includes an abrasive and a lubricant. The abrasive present on the surface of the magnetic layer satisfies the relationship 0.01≦H 15 /H 10 ≦0.3 where H 10  denotes the number of particles per unit area having a height less than 10 nm (particles/μm 2 ) and H 5  denotes the number of particles per unit area having a height equal to or greater than 15 nm (particles/μm 2 ). The magnetic recording medium has a surface lubricant index of 3 to 11. The height of the abrasive particles can be controlled by, for example, a blade treatment using an abrasive tape (LTBL system) or a diamond powder-studded rotating roll (DWBL system).

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a magnetic recording medium thathas a low level of head wear as well as little head contamination afterrunning.

[0003] 2. Description of the Related Art

[0004] Magnetic recording media have been widely used as sound recordingtapes, video tapes, computer tapes, disks, etc. The density of magneticrecording media has been increasing year by year, and the recordingwavelength has been decreasing. Moreover, recording systems fromanalogue systems to digital systems have been studied.

[0005] In particular, a magnetic recording medium in which aferromagnetic metal powder comprising mainly Fe is coated together witha binder on a non-magnetic support currently dominates the field ofmedia for video for broadcasting and data recording because of itsexcellent cost performance. In drives for video for broadcasting anddata recording, higher capacity together with higher speed of themagnetic recording medium relative to the magnetic head, the so-called‘higher transfer rate’, are being developed. In order to achieve ahigher capacity, it is necessary to increase the recording density, anda magnetic recording medium having excellent electromagnetic conversioncharacteristics is required. In systems in which a high capacity and ahigh transfer rate are realized, particularly in VTRs for broadcasting,an expensive head assembly is installed. Since the relative speedbetween head and tape is high in accordance with the high transfer rate,wear of the magnetic head seriously affects the maintenance and therunning costs of the above-mentioned systems, and there is therefore anintense demand for a magnetic recording medium that has a low level ofhead wear, thereby increasing the head lifespan.

BRIEF SUMMARY OF THE INVENTION

[0006] The present invention has been carried out in view of theabove-mentioned circumstances.

[0007] It is an object of the present invention to provide a magneticrecording medium that has a low level of head wear and is excellent interms of head contamination and still frame durability. A specificobject is to provide an excellent magnetic recording medium for a systemin which there is a high relative speed between tape and head and alarge area of tape is used per unit time, the magnetic recording mediumhaving low wear of the magnetic head and at the same time little headcontamination.

[0008] Usually, when the head wear is reduced, the head contaminationcharacteristics are impaired. With regard to means for reducing the headwear, there are known methods such as a method in which the type of anabrasive in the magnetic layer is changed to one having a lower abrasivepower or the amount thereof is reduced, a method in which thecomposition of an oxide film on the ferromagnetic metal powder isadjusted, and a method in which the kneading intensity duringpreparation of a magnetic liquid is optimized. However, these methodscannot fully overcome the above-mentioned trade-off relationship, andthe above-mentioned demand cannot be met.

[0009] As a result of an intensive investigation by the presentinventors in order to solve the mutually contradictory problems of headwear and head contamination, it has been found that the object can beaccomplished by a magnetic recording medium comprising a non-magneticsupport, and a magnetic layer formed on the support and comprisingmainly a binder resin and a ferromagnetic metal powder comprising mainlyFe, said magnetic layer comprising an abrasive and a lubricant, theabrasive present on the surface of the magnetic layer satisfying therelationship:

0.01≦H₁₅/H₁₀≦0.3

[0010] and the magnetic recording medium having a surface lubricantindex of 3 to 11, where H₁₀ denotes the number of particles per unitarea having a height less than 10 nm (particles/μm²), and H₁₅ denotesthe number of particles per unit area having a height equal to orgreater than 15 nm (particles/μm²).

[0011] The above-mentioned object, other objects, features, andadvantages of the invention will become clear from the followingdescription.

BRIEF DESCRIPTION OF THE DRAWING

[0012]FIG. 1 is a sketch of a blade treatment device employing an LTBLsystem.

[0013]FIG. 2 is a sketch of a blade treatment device employing a DWBLsystem.

DETAILED DESCRIPTION OF THE INVENTION

[0014] The present inventors have carried out a detailed examinationinto the relationship of head wear and head contamination to theprotrusion height of an abrasive and the amount of a lubricant that arepresent on the surface of a magnetic layer. As a result, it has beenfound that the smaller the height of abrasive particles protruding fromthe surface of the magnetic layer, the lower the level of head wear.Moreover, the presence of an appropriate amount of a lubricant on thesurface can reduce the sliding resistance between the head and the tape,thereby giving a yet lower level of head wear and maintaining the headcontamination at a suitable level.

[0015] It has also been found that the level of head wear dependsstrongly on the height of the abrasive protruding from the surface ofthe magnetic layer rather than the two-dimensional size of the abrasive,and the head wear can be reduced by having fewer high protrusions andhaving more low protrusions. That is, the head wear can be reduced andthe head lifespan can be increased when, among the abrasive particlesthat are present on the surface of the magnetic layer, the relationship0.01≦H₁₅/H_(10 ≦)0.3 can be satisfied, where H₁₀ is the number ofparticles having a height less than 10 nm per unit area and H₁₅ is thenumber of particles having a height equal to or greater than 15 nm perunit area, and it is preferable that 0.01≦H_(15/)H₁₀ 10≦0.2. When theratio H_(15/)H₁₀ is less than this range, there are too many lowprotrusions, that is, the packing density of a magnetic material on thesurface of the magnetic layer decreases, and the electromagneticconversion characteristics are therefore degraded; too small an amountof the high protrusions impairs the ability to remove deposits attachedto the head, thereby worsening the head contamination.

[0016] However, since the ability to clean the head drops as the headwear is lowered by controlling only the height that the abrasiveprotrudes from the surface of the magnetic layer, there is a tendencyfor head contamination to increase.

[0017] As a result of an investigation by the present inventors into thelubricant that is present on the surface of the magnetic layer, it hasbeen found that the amount of a surfactant on the surface and thesliding characteristics of the tape against the head are closely relatedto each other. Optimizing the amount of lubricant that is present on thesurface of the magnetic layer can reduce the sliding resistance betweenthe head and the tape, thus lowering the head wear and preventingdeposits from adhering to the head. When the surface lubricant index (anindex relating to the amount of lubricant on the surface of a magneticrecording medium measured by an Auger electron spectroscopy system; themeasurement method will be explained later) is in the range of 3 to 11(meaning at least 3 and at most 11; the same applies to the descriptionin the present invention below), the level of head wear can be reducedand the head contamination can be effectively suppressed. The index ispreferably in the range of 4 to 11. When the surface lubricant indexexceeds this range, since the surface of the magnetic layer isplasticized, the head contamination increases. When the surfacelubricant index is less than this range, since the sliding resistancebetween the head and the tape is not low enough, the head contaminationcannot be improved.

[0018] That is, adjusting only the height that the abrasive protrudesfrom the surface of the magnetic layer cannot prevent worsening of thehead contamination due to reduction of the head wear, but furtheroptimization of the amount of lubricant on the surface of the magneticlayer can overcome the above-mentioned trade-off relationship, and amagnetic recording medium having excellent characteristics in both headwear and head contamination can be achieved.

[0019] To control the distribution of height that the abrasiveprotrudes, the following methods can be cited as examples.

[0020] 1) Binder for dispersing the abrasive

[0021] With regard to a method in which the abrasive is dispersed in abinder and a solvent in advance, the dispersion is then added to amagnetic liquid containing no abrasive, and the mixture is thendispersed to give a magnetic coating solution, and a method in which anabrasive is dispersed in a binder and a solvent in advance, thisdispersion is then mixed with a dispersion of a magnetic liquidcontaining no abrasive, and the mixture is further dispersed ifnecessary to give a magnetic coating solution, the compatibility betweenthe binder for dispersing the abrasive and the binder in the magneticliquid containing no abrasive is varied. If the compatibility is high,it is possible to reduce the movement of the abrasive particles duringcoating and drying of a magnetic layer, thereby reducing the height thatthe abrasive protrudes. On the other hand, if the compatibility is low,the height that the abrasive protrudes increases.

[0022] 2) Strong pushing by a calender:

[0023] The surface of a magnetic layer is processed by means of a hardroll such as a metal roll at high pressure and high temperature to pushhighly protruding abrasive into the magnetic layer. The linear pressureis 2,000 to 4,500 N/cm (200 to 450 kg/cm), and preferably 2,500 to 4,000N/cm (250 to 400 kg/cm), and the processing temperature is 700° C. to110° C., and preferably 80° C. to 100° C. The processing speed is 50 to400 m/min, and preferably 80 to 300 m/min. If the linear pressure andthe processing temperature are much higher than the above ranges or theprocessing speed is much lower than the above range, the ratio H₁₅/H₁₀becomes low, and the transport durability deteriorates. If the linearpressure and the processing temperature are much lower than the aboveranges or the processing speed is much higher than the above range, theratio H₁₅/H₁₀ becomes high, thus increasing the level of head wear.

[0024] 3) Adjustment of the binder:

[0025] If the type and the proportion of the binder in the magneticlayer are adjusted to lower the Tg of the magnetic layer prior tocalendering, the ratio H₁₅/H₁₀ becomes low even when calendering isperformed under the same conditions. If the amount of binder relative tothe magnetic material is decreased to a degree that does not impair thedispersion, the voids in the magnetic layer prior to calenderingincrease, and the ratio H₁₅/H₁₀ can be decreased even when calenderingis performed under the same conditions.

[0026] 4) Kneading conditions:

[0027] When preparing a magnetic coating solution, kneading of amagnetic material, a binder, and a small amount of solvent is generallycarried out with a strong shear force by means of a device such as akneader. The kneading treatment increases the adsorptivity of themagnetic material and the binder, thus increasing the degree of packingof the magnetic layer and increasing the strength of the magnetic layer.Although strong kneading increases the degree of packing, the voids ofthe magnetic layer after coating decrease, thereby making calenderingdifficult and increasing the ratio H₁₅/H_(10.)

[0028] 5) Blade treatment:

[0029] A magnetic tape is lapped with an abrasive tape, or lapped with arotating roll studded with a hard powder such as a diamond powder topolish the magnetic layer or top-cut the protrusions of the abrasive.More specifically, a blade, system involving lapping with an abrasivetape (LTBL system), and a blade system involving lapping with a diamondpowder-studded rotating roll (DWBL system) can be employed, preferablyunder the conditions below. FIG. 1 is a sketch of a device employing theLTBL system. A magnetic tape 5 that has been transported is fed via afeed roll 4 to a sapphire blade 6 and polished. It is then taken up viaa feed roll 4, thus completing the treatment. Between the sapphire blade6 and the magnetic tape 5, a lapping tape 1 is transported by rotatingrolls 2 in a direction opposite to that in which the magnetic tape 5 istransported. This system is described in detail in JP-A-63-259830 (JP-Adenotes Japanese unexamined patent application publication).

[0030] The LTBL system can employ a lapping tape K-10000, MA-20000 orMS20000 manufactured by Fuji Photo Film Co., Ltd. It is preferable thatthe transport speed (V) of the magnetic tape is set at 3 to 20 m/sec andthat the transport speed (v) of the lapping tape is set at 10 to 50mm/min. The tension (T1) of the magnetic tape in region a in FIG. 1 ispreferably set at 30 to 50 g/(½ inch width), and the tension (T2) of themagnetic tape in region b in FIG. 1 is preferably set at 100 to 200 g/(½inch width), with a difference in tension (T2−T1) in the range of 50 to150 g/(½ inch width).

[0031]FIG. 2 is a sketch of a device employing the DWBL system. Amagnetic tape 5 that has been transported is fed via a feed roll 4 to arotating roll 3 studded with a diamond powder and is polished. Afterthat, it is feed roll 4, thus completing the treatment. The rotatingroll 3 rotates in a direction opposite to that in which the magnetictape 5 is transported. This system is described in detail inJP-A-62-172532.

[0032] As the rotating roll 3 used in the DWBL system, for example,DW#600, #800, or #1000 manufactured by Oriental Diamond Tools Lab. Co.,Ltd. (diameter: 7 cm, lap angle (0):90° C., Ra of #800: 0.5-1.3 μm) canbe used. The transport speed (V) of the magnetic tape and the tangentialspeed (v) of the rotating roll 3 are preferably set at 3 to 7 m/sec. Thetension (T1) of the magnetic tape at region a in FIG. 2 is preferablyset in the range of 30 to 150 g/(½ inch width), and the tension (T2) ofthe magnetic tape at region b in FIG. 2 is preferably set in the rangeof 100 to 300 g/(½ inch width), with a difference in tension (T2−T1) inthe range of 50 to 200 g/(½ inch width).

[0033] Next, the abrasive used in the magnetic layer of the presentinvention is explained in detail. An inorganic non-magnetic powder canbe used as the abrasive. Examples of the inorganic non-magnetic powderinclude inorganic compounds such as a metal oxide, a metal carbonate, ametal sulfate, a metal nitride, a metal carbide, and a metal sulfide. Asthe inorganic compound, α-alumina with an α-component proportion of 90%to 100%, β-alumina, γ-alumina, silicon carbide, chromium oxide, ceriumoxide, α-iron oxide, corundum, silicon nitride, titanium carbide,titanium oxide, silicon dioxide, tin oxide, magnesium oxide, tungstenoxide, zirconium oxide, boron nitride, zinc oxide, barium sulfate,molybdenum disulfide, etc. can be used singly or in combination.Particularly preferred are α-alumina, ferric oxide, and chromium oxide.Calcium carbonate is not desirable since it becomes a source of supplyof a water-soluble metal ion.

[0034] In the present invention, the abrasive is used by varying thetype, amount, particle size, combination, shape, etc. so that the ratioH₁₅/H₁₀, which denotes the protrusion height distribution of theabrasive present on the surface of the magnetic layer, is in theabove-mentioned range. When only one type of abrasive is used, theaverage particle size of the abrasive used in the present invention ispreferably 0.05 to 0.4 μm, and more preferably 0.1 to 0.3 μm. It ispreferable that particles with a particle size larger than the averageparticle size by 0.1 μm or more are present at a proportion of 1 to 40%,more preferably 5 to 30%,. and most preferably 10 to 20%. Although theparticle size of the abrasive itself affects the particle size ofabrasive particles that are actually present on the surface of themagnetic layer, they are not equal to each other. The particle size ofthe abrasive particles present on the surface of the magnetic layervaries according to the dispersion conditions, etc. for the abrasive.Furthermore, some particles come out easily to the surface of themagnetic layer during coating and drying steps whereas it is difficultfor others to come out to the surface.

[0035] Two or more abrasives having different average particle sizes maybe used in combination. In this case, taking the weighted average valueas the average particle size, which depends on the actual proportionsused of the two or more abrasives, the particles with a particle size0.1 μm or more greater than the average particle size can be set so asto be within the above-mentioned range. Changing the dispersionconditions for the two abrasives can also control the particle size. Forexample, abrasive A is dispersed with a binder and a solvent in advance.This dispersion and abrasive B as a powder are added to a kneadedferromagnetic metal powder that has been kneaded separately with abinder and a solvent, and the mixture is dispersed. In this way, thedispersion conditions for the abrasive A and the abrasive B can bevaried. That is, the abrasive A is dispersed more strongly than theabrasive B.

[0036] The tap density of the abrasive powder is 0.05 to 2 g/ml, andpreferably 0.2 to 1.5 g/ml. The water content of the abrasive powder is0.05 to 5 wt %, and preferably 0.2 to 3 wt %. The specific surface areaof the abrasive is 1 to 100 m²/g, and preferably 5 to 50 m²/g. Its oilabsorption determined using DBP is 5 to 100 ml/100 g, and preferably 10to 80 ml/100 g. The specific gravity is 1 to 12, and preferably 3 to 6.The shape of the abrasive may be any one of acicular, spherical,polyhedral, and tabular.

[0037] The surface of the abrasive may be coated at least partially witha compound which is different from the main component of the abrasive.Examples of the compound include Al₂O₃, SiO₂, TiO₂, ZrO₂, SnO₂, Sb₂O₃,and ZnO. In particular, the use of Al₂O₃, SiO₂, TiO₂ or ZrO₂ gives gooddispersibility. These compounds may be used singly or in combination.

[0038] Specific examples of the abrasive used in the magnetic layer ofthe present invention include Nanotite (manufactured by Showa Denko K.K. ), Hit 100, Hit 82, Hit 80, Hit 70, Hit 60A, Hit 55, AKP-20, AKP-30,AKP-50, and ZA-G1 (manufactured by Sumitomo Chemical Co., Ltd.),ERC-DBM, HP-DBM, HPF-DBM, HPFX-DBM, HPS-DBM, and HPSX-DBM (manufacturedby Reynolds Corp.), WA8000 and WA10000 (manufactured by FujimiIncorporated), UB20, UB40B, and Mecanox UA (manufactured by C. Uyemura &Co., Ltd.), UA2055, UA5155, and UA5305 (manufactured by Showa KeikinzokuK. K. ), G-5, Kromex M, Kromex S1, Kromex U2, Kromex U1, Kromex X10, andKromex KX10 (manufactured by Nippon Chemical Industry Co., Ltd.), ND803,ND802, and ND801 (manufactured by Nippon Denko Co., Ltd.), F-1, F-2, andUF-500 (manufactured by Tosoh Corporation), DPN-250, DPN-250BX, DPN-245,DPN-270BX, TF100, TF-120, TF-140, DPN-550BX, and TF-180 (manufactured byToda Kogyo Corp.), A-3 and B-3 (manufactured by Showa Mining Co., Ltd.),beta SiC and UF (manufactured by Central Glass Co., Ltd.), β-RandomStandard and β-Random Ultrafine (manufactured by Ibiden Co., Ltd.),JR401, MT-100S, MT-100T, MT-150OW, MT-500B, MT-600B, MT-100F, andMT-500HD (manufactured by Tayka Corporation), TY-50, TTO-51 B, TTO-55A,TTO-55B, TTO-55C, TTO-55S, TTO-55D, SN-100, E270, and E271 (manufacturedby Ishihara Sangyo Kaisha Ltd.), STT-4D, STT-30D, STT-30, STT-65C, andY-LOP and calcined products thereof (manufactured by Titan KogyoKabushiki Kaisha), FINEX-25, BF-1, BF-10, BF-20, and ST-M (manufacturedby Sakai Chemical Industry Co., Ltd.), HZn, and HZr3M (manufactured byHokkai Kagaku), DEFIC-Y and DEFIC-R (manufactured by Dowa Mining Co.,Ltd.), AS2BM and TiO2P25 (manufactured by Nippon Aerosil Co., Ltd.), and100A and 500A (manufactured by Ube Industries, Ltd.).

[0039] Next, the ferromagnetic metal powder comprising mainly iron thatis used in the present invention is explained.

[0040] The shape of the ferromagnetic metal powder used in the presentinvention is not particularly limited, and it can be acicular,spindle-shaped, spherical, chained spheres, cubic, tabular, etc. Amongthese, acicular and spindle-shaped are preferred.

[0041] When the shape is acicular or spindle-shaped, the average lengthof the major axis is 0.03 to 0.3 μm, and preferably 0.05 to 0.2 μm. Whenthe average length of the major axis exceeds this range, the magneticmaterial tends to aggregate, the packing ratio of the magnetic materialin the magnetic layer is thus decreased, the electromagnetic conversioncharacteristics deteriorate, and since the number of magnetic materialparticles that stand perpendicular to the surface of the coatingincreases, the head wear is accelerated. On the other hand, when theaverage length of the major axis is less than this range, the magneticparticles become too fine, thereby degrading the durability.

[0042] In the ferromagnetic metal powder comprising mainly iron, poresare formed within the particles during a process for the productionthereof. The pore level can be estimated from the specific surface area,and it is generally 35 to 70 m²/g in the present invention, andpreferably 40 to 60 m²/g. When the specific surface area is large, thepore level in the metal powder is high, the magnetic characteristicsdeteriorate, and the electromagnetic conversion characteristics areinadequate. Furthermore, when preparing a coating solution, theviscosity becomes high, thereby making it difficult to prepare thecoating solution. When the specific surface area of the particles isless than the above-mentioned range, the particle size is large, and theelectromagnetic conversion characteristics undesirably deteriorate.

[0043] The method for producing the ferromagnetic metal powder is notparticularly limited, and a conventionally known method can be employed;a method in which an oxide or hydrated oxide comprising mainly iron isreduced by heating it in a reducing gas is most preferred in terms ofboth performance and productivity.

[0044] The ferromagnetic metal powder preferably has an oxide film onthe surface. The oxide film can be formed by a slow oxidation treatmentof the surface after forming the ferromagnetic metal powder. With regardto the slow oxidation treatment, there are, for example, a method inwhich the powder is immersed in an organic solvent and then dried, amethod in which the powder is immersed in an organic solvent, anoxygen-containing gas is introduced so as to form an oxide film on thesurface and the powder is then dried, and a method in which an oxidefilm is formed on the surface of the powder by adjusting the partialpressures of oxygen gas and an inert gas without using any organicsolvent. The method involving a gas-phase reaction is preferred becausea uniform oxide film can be formed and the oxidation resistance isimproved.

[0045] The ferromagnetic metal powder used in the present inventioncomprising mainly Fe and can comprise any other element if necessary.For example, Al, Si, S, Ca, Ti, V, Cr, Cu, Mo, Rh, Pd, Ag, Sn, Sb, Te,Ba, Ta, W, Re, Au, Hg, Pb, Bi, P, Mn, Zn, Ni, Co, Sr, B, Y, La, Nd, Sm,Gd, etc. can be cited. Among these, the total amount of Ni and Co addedis preferably at most 50 atom % (relative to Fe), and more preferably 1to 40 atom %. The amount of an element other than Ni and Co added ispreferably 1 to 30 atom % (relative to Fe+Ni+Co), and more preferably 5to 20 atom %.

[0046] The crystallite size of the ferromagnetic metal powder used inthe present invention is usually about 100 to 250 Å, and preferably 130to 180 Å. The saturation magnetization (σS) is usually about 100 to 180A·m²/kg (100 to 180 emu/g), and preferably 120 to 160 A·m²/kg (120 to160 emu/g). The Hc can be determined according to the system used, andit is on the order of 1.11 ×10⁵ to 2.22×10⁵ A/m (1400 to 2800 Oe). ThepH is preferable Optimized according to the binder it will be used incombination with. Its range is 4 and preferably 7 to 11.

[0047] The ferromagnetic metal powder of the present inventionpreferably contains 0.1 to 2.0 wt % of water. The ferromagnetic metalpowder containing water can be prepared by contacting the ferromagneticmetal powder with a gas containing water or steam.

[0048] The ferromagnetic metal powder used in the magnetic recordingmedium of the present invention can be subjected, prior to dispersion,to a treatment with a dispersant, a lubricant, a surfactant, anantistatic agent, etc., which will be described below. Details aredescribed in JP-B-44-14090 (JP-B denotes a Japanese examined patentapplication publication), JP-B-45-18372, JP-B-47-22062, JP-B-47-22513,JP-B-46-28466, JP-B-46-38755, JP-B-47-4286, JP-B-47-12422,JP-B-47-17284, JP-B-47-18509, JP-B-47-18573, JP-B-39-10307,JP-B-48-39639, U.S. Pat. Nos. 3,026,215, 3,031,341, 3,100,194,3,242,005, 3,389,014, etc.

[0049] With regard to the binder used in the present invention,conventionally known thermoplastic resins, thermosetting resins,reactive type resins and mixtures thereof can be used. With regard tothe thermoplastic resins, those having a glass transition temperature of−20 to 90° C., a number-average molecular weight of 1,000 to 200,000,and preferably 10,000 to 100,000, and a degree of polymerization ofabout 50 to 1,000 can be cited. Examples of such binders includepolymers or copolymers containing, as a monomer unit, vinyl chloride,vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, an acrylateester, vinylidene chloride, acrylonitrile, methacrylic acid, amethacrylate ester, styrene, butadiene, ethylene, vinyl butyral, vinylacetal, a vinyl ether, etc., polyurethane resins and variousrubber-based resins. In addition, with regard to examples of thethermosetting resins and the reactive type resins, phenol resins, epoxyresins, polyurethane thermosetting type resins, urea resins, melamineresins, alkyd resins, acrylic-based reactive resins, formaldehyderesins, silicone resins, epoxy-polyamide resins, a mixture of apolyester resin and an isocyanate pre-polymer, a mixture of a polyesterpolyol and a polyisocyanate, a mixture of a polyurethane and apolyisocyanate, etc. can be cited. Details of these resins are given inthe ‘Plastic Handbook’, published by Asakura Publishing. Moreover, knownelectron beam curable resins can be used.

[0050] Examples of the above-mentioned binders and methods for theirproduction are described in detail in JP-A-62-256219. The resinsmentioned above can be used singly or in combination. As preferredresins, a combination of a polyurethane resin and at least one type ofresin selected from vinyl chloride resins, vinyl chloride-vinyl acetateresins, vinyl chloride-vinyl acetate-vinyl alcohol resins, and vinylchloride-vinyl acetate-maleic anhydride copolymers, or a furthercombination with a polyisocyanate can be cited. As the structure of thepolyurethane resin, known structures such as polyester-polyurethane,polyether-polyurethane, polyether-polyester-polyurethane,polycarbonate-polyurethane, polyester-polycarbonate-polyurethane,polycaprolactone-polyurethane and polyolefin-polyurethane can be used.With regard to all the binders mentioned above, in order to yet furtherimprove the dispersibility and durability, if necessary, it is preferredto incorporate at least one group selected from —COOM, —SO₃M, —OSO₃M,—P═O(OM¹)₂, —O—P═O(OM¹)₂ (where M denotes hydrogen or an alkali metalatom and M¹ denotes hydrogen, an alkali metal atom or a lowerhydrocarbon group), —OH, —NR₂, —N⁺R₃ (where R denotes a hydrocarbongroup having 1 to 12 carbons), an epoxy group, —SH, —CN, sulfobetaine,carboxybetaine, phosphobetaine, etc., and preferably at least one groupselected from —COOM, —SO₃M, —OSO₃M and —P═O(OM¹)₂ (M and M′ denote thesame as above), into at least one of a polyurethane resin and a vinylchloride based resin by copolymerization or an addition reaction. Theamount of such a polar group is 10⁻⁸ to 10⁻² mol/g, preferably 10⁻⁶ to10⁻² mol/g, and more preferably 3×10⁻⁵ to 20×10⁻⁵ mol/g.

[0051] Specific examples of these binders used in the present inventioninclude VAGH, VYHH, VMCH, VAGF, VAGD, VROH, VYES, VYNC, VMCC, XYHL,XYSG, PKHH, PKHJ, PKHC and PKFE manufactured by Union CarbideCorporation, MPR-TA, MPR-TA5, MPR-TAL, MPR-TSN, MPR-TMF, MPR-TS, MPR-TMand MPR-TAO manufactured by Nisshin Chemical Industry Co., Ltd., 1000W,DX80, DX81, DX82, DX83 and 100 FD manufactured by Denki Kagaku KogyoKabushiki Kaisha, MR-104, MR-105, MR-110, MR-100 and 400X-110Amanufactured by Nippon Zeon Corporation, Nippollan N2301, N2302 andN2304 manufactured by Nippon Polyurethane Industry Co., Ltd., PandexT-5105, T-R3080 and T-5201, Burnock D-400 and D-210-80 and Crisvon 6109and 7209 manufactured by Dainippon Ink and Chemicals, Inc., VylonUR-8200, UR-8300, UR-8600, UR-5500, UR-4300, RV-530, RV-280 and FB-84manufactured by Toyobo Co., Ltd., Daiferamine 4020, 5020, 5100, 5300,9020, 9022 and 7020 manufactured by Dainichiseika Color & Chemicals Mfg.Co., Ltd., MX 5004 manufactured by Mitsubishi Chemical Corporation,Sanprene SP-150, TIM-3003 and TIM-3005 manufactured by Sanyo ChemicalIndustries Co., Ltd., Saran F310 and F210 manufactured by Asahi KaseiCorporation, etc. Among those above, MR-104 and MR-110 are preferred.

[0052] Examples of the polyisocyanate used in the present inventioninclude isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethanediisocyanate, hexamethylene diisocyanate, xylylene diisocyanate,naphthylene-1,5-diisocyanate, o-toluidine diisocyanate, isophoronediisocyanate, and triphenylmethane triisocyanate; reaction products ofthese isocyanates with a polyalcohol; and polyisocyanates formed by anisocyanate condensation reaction. These isocyanates are commerciallyavailable under the trade names of Coronate L, Coronate HL, Coronate2030, Coronate 2031, Millionate MR and Millionate MTL (manufactured byNippon Polyurethane Industry Co., Ltd.), Takenate D-102, TakenateD-110N, Takenate D-200 and Takenate D-202 (manufactured by TakedaChemical Industries, Ltd.), and Desmodur L, Desmodur IL, Desmodur N andDesmodur HL (manufactured by Sumitomo Bayer Urethane Co., Ltd.). Theseisocyanates may be used singly or in combination.

[0053] The binders used in the magnetic layer of the present inventionare used in an amount of 10 to 30 wt %, and preferably 15 to 25 wt %,relative to the ferromagnetic metal powder. In particular, a combinationof a vinyl chloride based resin, a polyurethane and a polyisocyanate ispreferably used. When these three components are used together, thevinyl chloride based resin is used in an amount of 5 to 20 wt %, andpreferably 7 to 15 wt %, the polyurethane resin is used in an amount of2 to 15 wt %, and preferably 4 to 10 wt % and the polyisocyanate is usedin an amount of 2 to 20 wt %, and preferably 3 to 10 wt %. The totalamount of the three components is 10 to 30 wt %, and preferably 15 to 25wt %. Thus, a ferromagnetic metal powder is dispersed well in a vinylchloride based resin, flexibility is imparted to the magnetic layer bymeans of a polyurethane, and the magnetic layer is cross-linked with apolyisocyanate to give a tough magnetic layer.

[0054] A most preferred polyurethane in the present invention is apolyurethane having as main components a diol component consisting of apolyether polyol and a polyester polyol, and a polyisocyanate component(hereinafter, called a ‘preferred polyurethane’).

[0055] With regard to the structure of the polyether polyol of thepreferred polyurethane, those having, as a basic component, PPG(polypropylene glycol), PTMG (polytetramethylene glycol), PEG(polyethylene glycol), a BPA (bisphenol A) adduct with PO (propyleneoxide) and/or EO (ethylene oxide) and a mixture thereof can be cited.PPG and PTMG are particularly preferred.

[0056] The Tg of the polyether polyol is 0° C. or less, and preferably−10 to −60° C. The molecular weight thereof is usually 400 to 10,000,preferably 500 to 5,000, and more preferably 800 to 3,000. Theproportion of the polyether polyol in the polyurethane is usually 3 to80 wt %, preferably 5 to 70 wt %, and more preferably 10 to 50 wt %.When this proportion is too small, the effect becomes small. When it istoo large, the mechanical strength is degraded and the durability isimpaired.

[0057] With regard to the structure of the polyester polyol of thepreferred polyurethane, those containing a monomer having a cyclicstructure (aromatic or alicyclic) and having a branched structure arepreferred. With regard to the acid components, isophthalic acid (iPA),terephthalic acid, etc. can be cited. With regard to the alcoholcomponents, neopentyl glycol (NPG), cyclohexanedimethanol (CHM),cyclohexanediol, bisphenol A, hydrogenated bisphenol A, etc. arepreferred. The molecular weight of the polyester polyol is usually 400to 10,000, preferably 500 to 5,000, and more preferably 800 to 3,000.

[0058] The preferred polyurethane has at least two Tgs. One thereof isusually from −250° C. to 10° C., and preferably −200° C. to 10° C.Another thereof is usually from 40 to 130° C., and preferably 45° C. to110° C. When it has two Tgs, the lower one (low Tg) is preferably −5° C.or less, and more preferably −10° C. to −400° C. The higher one (highTg) is preferably 50° C. to 120° C., and more preferably 60 to 100° C. Apolyurethane having at least three Tgs can be prepared using either twodifferent types of polyester polyol component and one type of polyetherpolyol component or one type of polyester polyol component and two typesof polyether polyol component. One having at least four Tgs can also beprepared in the same manner as above. The Tg of the polyurethane is theE″ peak temperature of a film having a thickness of 20 μm measured usinga Vibron (Orientech).

[0059] Such a preferred polyurethane can also have a low molecularweight polyol component such as a known chain propagating agent inaddition to the above-mentioned diol component. Specifically, apolyurethane having a branched structure can be formed using acombination of a diol such as NPG, ethylene glycol (EG), 1,4-butanediol(BD) or the dihydroxyethyl ether of bisphenol A and a tri- orhigher-functional alcohol such as trimethylolpropane. These componentscan be added at 0 to 40 wt % relative to the polyurethane.

[0060] With regard to the polyisocyanate components used for thepreferred polyurethane, aromatic and alicyclic diisocyanates such astolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI),isophorone diisocyanate (IPDI) and hydrogenated MDI are preferred.

[0061] The reason for the effect of the present invention being greatlyheightened by the use of the preferred polyurethane is described below.

[0062] As mentioned above, as one of the methods for controlling theprotrusion height distribution of the abrasive on the surface of themagnetic layer, there is a method in which the Tg of the binder used iscontrolled. In order to reduce the abrasive having a high protrusionheight, it is preferable to reduce the Tg of the binder. However, whenthe Tg of the binder is low, the Tg of the magnetic layer in themagnetic coating also becomes low, and the magnetic layer is more easilydestroyed by heat generated when the head and the tape slide againsteach other at high speed, thus easily degrading the transport durabilityby causing, for example, head clogging.

[0063] The preferred polyurethane is a polyurethane having both apolyether block and a polyester block, the polyurethane being formedfrom a polyether polyol component having a low Tg and a polyester polyolcomponent having a high Tg. Here, since the low Tg polyether polyol andthe high Tg polyester polyol have poor compatibility with each other,the polyurethane so formed undergoes micro phase separation in thepolyurethane film so as to form a low Tg phase that is soft and easilystretched and a high Tg phase that is hard. This can be confirmed byexamining the temperature dependence of the dynamic viscoelasticity,when peaks appear at two places in the loss modulus (E″) and the tan δ,which reflect the glass transition. Because of this it is possible tomaintain heat resistance and strength by means of the hard phase andrealize a high degree of stretch by means of the soft phase.

[0064] The ‘magnetic layer comprising mainly a binder resin and aferromagnetic metal powder’ referred to in the present invention meansthat the ferromagnetic metal powder and the binder resin are componentsessential for formation of the magnetic layer, and the abrasive,lubricant and other components are optional components.

[0065] Components of the magnetic layer other than the abrasive,ferromagnetic metal powder, and binder are now explained.

[0066] The magnetic layer of the present invention can contain a powdersuch as carbon black. Examples of the carbon black used in the presentinvention include furnace black for rubber, thermal black for rubber,black for coloring, and acetylene black. The carbon black preferably hasa specific surface area of 5 to 500 m²/g, a DBP oil absorption of 10 to400 ml/100 g, a particle size of 5 to 300 nm, a pH of 2 to 10, a watercontent of 0.1 to 10%, and a tap density of 0.1 to 1.0 g/ml. Specificexamples of the carbon black used in the present invention includeBLACKPEARLS 2000, 1300, 1000, 900, 800, and 700, and VULCAN XC-72(manufactured by Cabot Corporation), #80, #60, #55, #50, and #35(manufactured by Asahi Carbon Co., Ltd.), #2400B, #2300, #5, #900, #950,#970, #1000, #30, #40 and #10B (manufactured by Mitsubishi ChemicalCorporation), and CONDUCTEX SC, RAVEN 150, 50, 40, and 15 (manufacturedby Columbian Carbon Co.). The carbon black may be subjected to any of asurface treatment with a dispersant, etc., grafting with a resin, and apartial surface graphitization. The carbon black may also be dispersedin a binder prior to addition to a magnetic coating solution. The carbonblack may be used alone or in combination. When the carbon black isused, it is preferably used in an amount of 0.1 to 30 wt % based on theamount of the magnetic material. The carbon black has the functions ofpreventing static buildup of the magnetic layer, reducing thecoefficient of friction, imparting light-shielding properties, andimproving the film strength. Such functions vary depending upon the typeof carbon black. Accordingly, it is of course possible in the presentinvention to appropriately choose the type, the amount and thecombination of carbon black as desired according to the intended purposeon the basis of the above-mentioned various properties such as theparticle size, the oil absorption, and the pH value, and electricalconductivity. Regarding carbon black for use in the magnetic layer ofthe present invention, for example, those described in the ‘Carbon BlackHandbook’ (edited by the Carbon Black Association of Japan) can bereferred to.

[0067] In the present invention, an additive having a lubricatingeffect, an antistatic effect, a dispersing effect, a plasticizingeffect, etc. may be used. Examples thereof include molybdenum disulfide,tungsten disulfide, graphite, boron nitride, graphite fluoride, asilicone oil, a polar group-containing silicone, a fatty acid-modifiedsilicone, a fluorine-containing silicone, a fluorine-containing alcohol,a fluorine-containing ester, a polyolefin, a polyglycol, an alkylphosphate and an alkali metal salt thereof, an alkyl sulfate and analkali metal salt thereof, polyphenyl ether, a fluorine-containing alkylsulfate and an alkali metal salt thereof, a monobasic fatty acid having10 to 24 carbons (which may contain an unsaturated bond and may bebranched) and a metal salt thereof (with Li, Na, K, Cu, etc.), a mono-,di-, tri-, tetra-, penta- or hexa-hydric alcohol having 12 to 22 carbons(which may contain an unsaturated bond and may be branched), an alkoxyalcohol having 12 to 22 carbons, a mono-, di- or tri-fatty acid esterformed from a monobasic fatty acid having 10 to 24 carbons (which maycontain an unsaturated bond and may be branched) and any one of mono-,di-, tri-, tetra-, penta- and hexa-hydric alcohols having 2 to 12carbons (which may contain an unsaturated bond and may be branched), afatty acid ester of a monoalkyl ether of an alkylene oxide polymer, afatty acid amide having 8 to 22 carbons, and an aliphatic amine having 8to 22 carbons.

[0068] Specific examples of the additive include lauric acid, myristicacid, palmitic acid, stearic acid, behenic acid, butyl stearate, oleicacid, linolic acid, linolenic acid, elaidic acid, octyl stearate, amylstearate, isooctyl stearate, octyl myristate, butoxyethyl stearate,anhydrosorbitan monostearate, anhydrosorbitan distearate,anhydrosorbitan tristearate, oleyl alcohol, and lauryl alcohol.Furthermore, examples of other additives that can be used include anonionic surfactant such as an alkylene oxide type, a glycerol type, aglycidol type, or an alkylphenol-ethylene oxide adduct; a cationicsurfactant such as a cyclic amine, an ester amide, a quaternary ammoniumsalt, a hydantoin derivative, a heterocyclic compound, a phosphoniumsalt, or a sulfonium salt, an anionic surfactant containing an acidicgroup such as a carboxylic acid, a sulfonic acid, a phosphoric acid, asulfate ester group, or a phosphate ester group; and an amphotericsurfactant such as an amino acid, an aminosulfonic acid, a sulfate esteror a phosphate ester of an amino alcohol, or an alkylbetaine. Details ofthese surfactants are described in the ‘Surfactant Handbook’ (publishedby Sangyo Tosho Publishing). The lubricant, antistatic agent, etc. neednot always be 100% pure and may contain, in addition to the maincomponent, an impurity such as an isomer, an unreacted material, abyproduct, a decomposed product, or an oxide. However, the impuritycontent is preferably 30 wt % or below, and more preferably 10 wt % orbelow.

[0069] In the present invention, the types and amounts of theselubricants and surfactants can be chosen as necessary. For example,bleeding out of the fatty acids to the surface may be controlled byusing fatty acids having different melting points from each other;bleeding out of the esters to the surface may be controlled by usingesters having boiling points and polarities that are different from eachother; and the coating stability may be enhanced by controlling theamount of surfactant, but the examples are by no means limited thereto.

[0070] All or a part of the additives used in the present invention maybe added to a magnetic coating solution at any stage of its preparation.For example, an additive may be blended with a ferromagnetic powderbefore a kneading step; it may be added during the kneading stepinvolving the ferromagnetic powder, a binder, and a solvent; it may beadded during a dispersing step; it may be added after the dispersingstep; or it may be added immediately before coating. Depending on theintended purpose, the purpose might be achieved by coating a part or allof the additives simultaneously with the magnetic layer or in successionafter coating the magnetic layer. Depending on the intended purpose, thelubricant may be coated on the surface of a magnetic layer after acalendering treatment or after completion of slitting.

[0071] Examples of commercially available lubricants used in the presentinvention include NAA-102, NAA-415, NAA-312, NAA-160, NAA-180, NAA-174,NAA-175, NAA-222, NAA-34, NAA-35, NAA-171, NAA-122, NAA-142, NAA-160,NAA-173K, hardened castor oil fatty acids, NAA-42, NAA-44, Cation SA,Cation MA, Cation AB, Cation BB, Nymeen L-201, Nymeen L-202, NymeenS-202, Nonion E-208, Nonion P-208, Nonion S-207, Nonion K-204, NonionNS-202, Nonion NS-210, Nonion HS-206, Nonion L-2, Nonion S-2, NonionS-4, Nonion O-2, Nonion LP-20R, Nonion PP-40R, Nonion SP-60R, NonionOP-80R, Nonion OP-85R, Nonion LT-221, Nonion ST-221, Nonion OT-221,Monogly MB, Nonion DS-60, Anon BF, Anon LG, butyl stearate, butyllaurate, and erucic acid (manufactured by NOF Corporation), oleic acid(manufactured by Kanto Kagaku), FAL-205, FAL-123 and Pionin E-818(manufactured by Takemoto Oil & Fat Co., Ltd.), Enujelv LO, Enujolv IPM,and Sansosyzer E4030 (manufactured by New Japan Chemical Co., Ltd.),TA-3, KF-96, KF-96L, KF-96H, KF-410, KF-420, KF-965, KF-54, KF-50,KF-56, KF-907, KF-851, X-22-819, X-22-822, KF-905, KF-700, KF-393,KF-857, KF-860, KF-865, X-22-980, KF-101, KF-102, KF-103, X-22-3710,X-22-3715, KF-910, and KF-3935 (manufactured by Shin-Etsu Chemical Co.,Ltd.), Armide P, Armide C, and Armoslip CP (manufactured by Lion ArmourCo., Ltd.), Duomin TDO (manufactured by Lion Corporation), BA-41G(manufactured by The Nisshin Oil Mills, Ltd.), and Profan 2012E, NewpolPE 61, lonet MS-400, lonet MO-200, lonet DL-200, lonet DS-300, lonetDS-1000 and lonet DO-200 (manufactured by Sanyo Chemical Industries,Ltd.).

[0072] If an organic phosphorus compound having a molecular weight of300 or less is used as an additive, the binding force and the amount ofthe ferromagnetic metal powder bound to the binder of the presentinvention are further increased so resulting in improved dispersibilityand reduced head wear and a decrease in the amount of binder that is notadsorbed on the ferromagnetic metal powder, and the durability of themagnetic recording medium can thus be enhanced outstandingly.

[0073] With regard to the organic phosphorus compounds, for example,compounds described in JP-A-1-189025 such as monophenyl phosphateC₆H₅OPO(OH)₂, mono-n-butyl phosphate n-C₄H₉OPO(OH)₂, dibutyl phosphite(C₄H₉O)₂P(OH), phenylphosphonic acid C₆H₅PO(OH)₂, etc. can be cited.

[0074] The thickness of the magnetic recording medium of the presentinvention is usually formed from a non-magnetic support having athickness of 1 to 100 μm, and preferably 4 to 12 μm, a magnetic layerusually having a thickness of 0.1 to 5 μm, and preferably 1 to 4 μm, anda backcoat layer usually having a thickness of 0.1 to 2 μm, andpreferably 0.4 to 1 μm and, for the purpose of improving adhesionbetween the non-magnetic support and the magnetic layer, an adhesivelayer having a thickness of 0.01 to 2 μm, and preferably 0.02 to 0.5 μm.A known adhesive layer and a known backcoat layer can be used in thiscase.

[0075] With regard to the non-magnetic support used in the presentinvention, known films such as polyethylene terephthalate, polyethylenenaphthalate, polyamide, polyimide, polyamide imide, aromatic polyamide,and polybenzimidazole can be used. In particular, a non-magnetic supportusing polyethylene terephthalate, polyethylene naphthalate, or an aramidresin is preferred.

[0076] These non-magnetic supports can be subjected in advance to acorona discharge treatment, a plasma treatment, a treatment forenhancing adhesion, a thermal treatment, a dust removal treatment, etc.In order to achieve the object of the present invention it is necessaryfor the surface roughness of the non-magnetic support to be 2 to 30 nm,preferably 5 to 25 nm, and more preferably 10 to 20 nm. In addition, itis preferable for these non-magnetic supports not only to have a smallcenter line average surface roughness but also to have no coarseprotrusions having a height of 1 μm or more. Furthermore, the surfaceroughness can be freely controlled by the size and amount of a fillerthat is added, if necessary, to the non-magnetic support. With regard toexamples of such a filler, either crystalline or amorphous oxides andcarbonates of Al, Ca, Si, Ti, etc., and acrylic-based and melamine basedorganic fine powders, etc. can be cited. In order to achievecompatibility with transport durability, it is preferable that theroughness of the side of the support on which the backcoat layer iscoated is higher than that of the side of the support on which themagnetic layer is coated.

[0077] However, it does not matter whether the surface roughness of theside of the non-magnetic support on which the backcoat layer is coatedis the same as or different from that of the side on which the magneticlayer is coated. If differentiating the roughness, a support having adual structure can be used or a coated layer can be formed.

[0078] The F-5 value of the non-magnetic support used in the presentinvention is preferably 70 to 300 MPa (7 to 30 kg/mm²) in both the tapetransport direction and the tape width direction. The F-5 value in thetape longitudinal direction is normally higher than that in the tapewidth direction, but it is not limited thereby if a particularly highstrength is required in the width direction. In addition, the thermalshrinkage of the non-magnetic support in the tape transport directionand in the tape width direction at 1000° C. for 30 minutes is preferably3% or less, and more preferably 1.5% or less, and the thermal shrinkageat 80° C. for 30 minutes is preferably 1% or less, and more preferably0.5% or less. The tensile strength in both directions is preferably 50to 1,000 MPa (5 to 100 kg/mm²) and the modulus of elasticity ispreferably 1,000 to 20,000 MPa (100 to 2,000 kg/mm²). In addition, thelight transmittance at a wavelength of 900 nm in the present inventionis preferably 30% or less, and more preferably 3% or less.

[0079] In order to achieve the object of the present invention, themagnetic recording medium is produced by known techniques, that is tosay, preparing a magnetic coating solution, coating this on anon-magnetic support, orienting, drying and subjecting it to a surfacesmoothing treatment, and slitting it into a predetermined width.

[0080] The magnetic coating solution is prepared by kneading anddispersing a ferromagnetic powder, a binder, carbon black, an abrasive,an antistatic agent, a lubricant, etc., usually with a solvent. Withregard to the solvent used in the kneading and dispersing, a solventsuch as methyl ethyl ketone, toluene, butyl acetate or cyclohexanone,which are usually used for the preparation of a magnetic coatingsolution, can be used. The method used for kneading and dispersing isnot particularly limited as long as it is one usually used for thepreparation of a magnetic coating solution. The order in which thecomponents are added can be set as appropriate. Moreover, it is alsopossible to pre-disperse part of the components in advance beforeaddition, or alternatively the components can be separately dispersedand then mixed with each other.

[0081] A normal kneader such as a two roll mill, a three roll mill, aball mill, a sand grinder, an attritor, a high-speed impeller dispersingmachine, a high-speed stone mill, a high-speed impact mill, a disper, akneader, a high-speed mixer, a homogenizer, or an ultrasonic dispersingmachine can be used for the preparation of the magnetic coatingsolution. Details of techniques for kneading and dispersing aredescribed in, for example, ‘Paint Flow and Pigment Dispersion’ by T. C.Patton (John Wiley & Sons, 1964) and ‘Industrial Materials (KogyoZairyo)’ Vol. 25, p. 37 (1977) by Shinichi Tanaka. They are alsodescribed in U.S. Pat. Nos. 2,581,414 and 2,855,515. A magnetic coatingsolution can also be prepared in the present invention by kneading anddispersing in accordance with the methods described in theabove-mentioned references.

[0082] The magnetic coating solution thus prepared is coated on theabove-mentioned non-magnetic support. In this stage, the dry thicknessof the magnetic layer is controlled so as to be preferably 0.05 to 10μm, and more preferably 0.2 to 5.0 μm. In the case of a structure withmultiple layers, a plurality of magnetic coating solutions are coatedsequentially or simultaneously by multilayer coating. With regard to thecoating machine for coating the above-mentioned magnetic coatingsolution, an air doctor coater, a blade coater, a rod coater, anextrusion coater, an air knife coater, a squeeze coater, an immersioncoater, a reverse roll coater, a transfer roll coater, a gravure coater,a kiss coater, a cast coater, a spray coater, a spin coater, etc. can beemployed. With respect to these coating machines, for example, ‘LatestCoating Technology’ published by Sogo Gijutsu Center Co. Ltd., (May 31,1983) can be referred to.

[0083] The coated layer obtained by coating the magnetic coatingsolution in this way is dried after subjecting the ferromagnetic powdercontained in the layer coated with the magnetic coating solution to anorientation treatment with a magnetic field. The orientation treatmentwith a magnetic field is preferably carried out using a solenoid of atleast 1.25 T (1,000 Gauss) in combination with a cobalt magnet of atleast 2.51 T (2,000 Gauss) disposed so that magnetic poles of the sametype face each other. Furthermore, it is preferable to provide a stepinvolving an appropriate degree of drying before the orientationtreatment so as to optimize the orientation after drying.

[0084] A backcoat layer can be formed on the side of the non-magneticsupport on which a magnetic coating solution has not been coated. Thebackcoat layer is usually a layer that is formed by coating a backcoatcoating solution, in which a binder and particulate components such asan abrasive and an antistatic agent are dispersed in an organic solvent,on the side of the non-magnetic support on which a magnetic coatingsolution is not coated. Moreover, an adhesive layer can be provided onthe sides of the non-magnetic support on which a magnetic coatingsolution and a backcoat layer coating solution are coated.

[0085] Coating of the backcoat layer is preferably carried out aftercoating and drying the magnetic coating solution, but it can be carriedout before coating the magnetic coating solution or after surfacesmoothing, which will be described below.

[0086] After the coated layer so formed is dried, it is subjected tosurface smoothing. The surface smoothing employs, for example, a supercalender, etc. The surface smoothing can eliminate voids generated byremoving the solvent during drying so improving the packing ratio of theferromagnetic powder in the magnetic layer, and a magnetic recordingmedium having high electromagnetic conversion characteristics can thusbe obtained. With regard to the calender roll, various types of metalroll and heat-resistant plastic rolls such as those made of epoxy,polyimide, polyamide and polyimide amide are used. With regard to thecalendering conditions, the temperature of the calender rolls is 600° C.to 1500° C., preferably 700° C. to 130° C., and particularly preferably800° C. to 110° C. The pressure is 1,000 to 5,000 N/cm (100 to 500kg/cm), preferably 2,000 to 4,500 N/cm (200 to 450 kg/cm), andparticularly preferably 2,500 to 4,000 N/cm (250 to 400 kg/cm).

[0087] After the calendering, the sample is subjected to a thermaltreatment. The thermal treatment can be carried out at a temperatureranging from 40° C. to 80° C. for 6 to 120 hours.

[0088] Thereafter, the sample is cut into a desired width using acutting machine such as a slitter. Furthermore, before or after cutting,the surface of the magnetic layer can be sublected to a blade treatmentusing a sapphire blade, etc.

[0089] With regard to the magnetic characteristics of the magneticrecording medium of the present invention, when measured in a magneticfield of 7.96×10² kA/m (10 kOe) using a VSM (vibrating sample masquareness ratio in the tape transport direction is at least 0.70,preferably at least 0.75, and more preferably at least 0.80. Thesquareness ratio in two directions that are perpendicular to the tapetransport direction is preferably at most 80% of that in the transportdirection. The SFD (switching field distribution) of the magnetic layeris preferably at most 0.7, and more preferably at most 0.6.

[0090] The surface roughness Ra of the magnetic layer is preferably 1 to10 nm, but it should be set appropriately according to the intendedpurpose. In order to improve the electromagnetic conversioncharacteristics the Ra is preferably smaller, whereas in order toimprove the transport durability the Ra is preferably larger. The RMSsurface roughness (RRMS) obtained by evaluation using AFM is preferablyin the range of 2 to 15 nm.

[0091] The coefficient of friction between SUS 420J and each of thesurface of the magnetic layer and the back surface of the magneticrecording medium of the present invention is preferably 0.1 to 0.5, andmore preferably 0.2 to 0.3. The surface resistivity is preferably 10⁴ to10¹² ohm/sq. The modulus of elasticity of the magnetic layer at 0.5%elongation is preferably 1,000 to 20,000 MPa (100 to 2,000 kg/mm) inboth the transport and width directions. The tensile strength ispreferably 10 to 300 MPa (1 to 30 kg/cm²). The modulus of elasticity ofthe magnetic recording medium is preferably from 1,000 to 15,000 MPa(100 to 1,500 kg/mm) in both the transport and width directions. Theresidual elongation is preferably at most 0.5%. The thermal shrinkage atany temperature up to and including 100° C. is preferably at most 1%,more preferably at most 0.5%, yet more preferably at most 0.1%, andideally 0%. The glass transition temperature (the temperature at whichthe loss modulus in a dynamic viscoelasticity measurement at 110 Hz is amaximum) of the magnetic layer is preferably 50° C. to 120° C. The lossmodulus is preferably in the range of 1×10⁷ to 8×10⁸ Pa (1×10⁸ to 8×10⁹dyne/cm²), and the loss tangent is preferably at most 0.2. When the losstangent is too large, cohesive failure easily occurs.

[0092] The amount of residual solvent contained in the magnetic layer ispreferably at most 100 mg/m², and more preferably at most 10 mg/m². Thevoid ratio of the magnetic layer is preferably at most 40 vol %, andmore preferably at most 30 vol %. A lower void ratio is preferred forattaining a higher output but, depending on the intended purpose, insome cases it is better to maintain a certain level of void ratio. Forexample, in the case of a magnetic recording medium for recording datain which repetitive use is considered to be important, a higher voidratio often gives better transport durability.

[0093] The magnetic recording medium of the present invention has atleast one magnetic layer but, depending on the intended purpose, it ispossible for it to have a multilayered structure. It is also possible toform a non-magnetic layer comprising at least a non-magnetic powder anda binder between the magnetic layer and the non-magnetic support. It caneasily be expected that, among the layers, various types of physicalcharacteristic can be made different from each other. For example, themagnetic layer can be made to have a high modulus of elasticity toimprove the transport durability while the elastic modulus of thenon-magnetic layer can be made lower than that of the magnetic layer,thereby improving contact between the head and the magnetic recordingmedium.

[0094] The magnetic recording medium that has an abrasive present on thesurface of the magnetic layer with an H₁₅/H¹⁰ in the range defined inthe present invention and that has a lubricant index in the rangedefined in the present invention has low head wear and exhibitsexcellent effects in terms of head contamination and still framedurability.

EXAMPLE

[0095] The present invention is described in detail below with referenceto specific examples, but it should not be construed as being limitedthereto. It should be noted that the designation ‘parts’ in the examplesmeans ‘parts by weight’.

[0096] Preparation of Magnetic Tape

[0097] Magnetic layer composition

[0098] 100 parts of a ferromagnetic metal powder was ground in an openkneader for 10 minutes. Next, the following components were added to thekneader and they were then kneaded for 60 minutes. Carbon black (averageparticle size 80 nm)  2 parts Vinyl chloride based resin 10 parts(MR-110 manufactured by Nippon Zeon Corporation) Polyester polyurethane 6 parts (solid portion) (UR-8300 manufactured by Toyobo Co., Ltd.)Methyl ethyl ketone/Cyclohexanone = 1/1 60 parts

[0099] 200 parts of methyl ethyl ketone/cyclohexanone (1/1) was thenadded over 6 hours to the mixture so kneaded while operating the openkneader.

[0100] Next, a dispersion of α-Al₂O₃ (see Table 1) was added thereto anddispersed in a sand grinder for 120 minutes.

[0101] Furthermore, the following components were added to the sandgrinder and mixed while stirring for 20 minutes. Polyisocyanate  4 parts(solid portion) (Coronate 3041 manufactured by Nippon PolyurethaneIndustry Co., Ltd.) Stearic acid  1 part sec-Butyl stearate See Table 1Stearamide  0.2 parts Toluene 50 parts

[0102] The mixture was then filtered using a filter having an averagepore size of 1 μm to give a magnetic coating solution.

[0103] The magnetic coating solution so obtained was coated on thesurface of a PET support having a thickness of 11 μm so as to have a drycoat thickness of 3 μm using an extrusion type coating head andsubjected to magnetic field orientation using magnet of 300 mT (3,000Gauss) before the magnetic coating solution had dried. The backcoatsolution described below was then coated and dried so as to have a drycoat thickness of 0.5 μm.

[0104] Subsequently, the sample was subjected to five stage calenderingusing a combination of metal and heat-resistant plastic rolls (speed 200m/min, linear pressure 3,000 N/cm (300 kg/cm), temperature 60° C. to100° C.). The roll so obtained was subjected to a thermal treatment at65° C. for 24 hours. The sample was then slit to a width of ½ inch at aspeed of 200 m/min.

[0105] The magnetic tape so slit was subjected to a blade treatmentusing an abrasive tape (MS-20000, manufactured by Fuji Photo Film Co.,Ltd.) at a out-feed tension of 40 g/ ½ inch to give a magnetic tape.

[0106] Composition of Backcoat solution Carbon black B (particle size 18nm)   100 parts Nitrocellulose   60 parts (HIG 1/2 manufactured by AsahiKasei Corporation) Polyurethane   60 parts (N-2301 manufactured byNippon Polyurethane Industry Co., Ltd.) Polyisocyanate   20 parts(Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd.)Methyl ethyl ketone 1,000 parts Toluene 1,000 parts

[0107] Evaluation of Characteristics of Magnetic Recording Medium

[0108] The characteristics of the video tape so produced were evaluatedby the measurement methods below, and the results are given in thetable.

[0109] Measurement method

[0110] 1. Height distribution of abrasive on surface of magnetic layer

[0111] The height distribution of the abrasive was measured using anatomic force microscope (Nanoscope AFM, manufactured by DigitalInstruments). Measurement was carried out using a regular tetrahedralcontact mode probe with tip half angle of 35° and a radius of curvatureof 100 nm or below using Ver. 3.25 software. The test sample was a 15μum×15 μm square, and the measurement result was corrected forinclination, etc. by third-order correction, and processed using acommand for obtaining the number of peaks in a Roughness Analysis togive the protrusion distribution.

[0112] 2. Surface lubricant index

[0113] A sample was divided into two, part (a) was left as it was andpart (b) was subjected to the method below in order to remove thelubricant component. Both samples were introduced into an Auger electronspectroscopy system (Model PHI-660, manufactured by Φ USA) and scannedthree times from kinetic energy 130 eV to 730 eV, with a primaryelectron beam acceleration voltage of 3 kV, a sample current of 130 mA,a magnification of 250 times and an inclination angle of 30°. Theintensities of carbon (C) KLL and iron (Fe) LMM peaks were obtained indifferential form to give the C/Fe ratio. The intensity ratio of (a) to(b) (C/Fe of (a) / C/Fe of (b)) was calculated and used as the surfacelubricant index.

[0114] Method for removing lubricant component: A sample (12.5 mm×30 mm)was immersed in n-hexane at room temperature for 30 minutes so as toextract and remove unadsorbed fatty acid and fatty acid ester. Thesample was then placed in a sample bottle; 10 ml of n-hexane and 0.3 mlof the silylating agent mixture TMSI-H (hexamethyl disilazane) (2): TMCS(trimethyl chlorosilane) (1): pyridine (10) was added thereto, and aderivatization reaction was carried out by heating at 60° C. for 1 hour.The sample was taken out, washed with ethanol, and then dried, thusremoving the lubricant component.

[0115] 3. Headwear

[0116] A D3VTR (D350, manufactured by Matsushita Electric IndustrialCo., Ltd.) was used; a 90 minute long tape was recorded and played backat 21° C. and 50% RH for 10 cycles continuously, the wear of each headwas measured and an average value was obtained.

[0117] 4. Head contamination

[0118] When measuring the above-mentioned head wear, the state ofcontamination of the head after running for 10 cycles was evaluatedusing the four criteria below.

[0119] A: No contamination

[0120] B: Slightly contaminated

[0121] C: Contaminated

[0122] D: Head gap contaminated

[0123] (Test results) TABLE 1 α-alumina Abrasive on dispersion Estermagnetic Surface Head Head Amount Amount layer surface lubricant wearcontamina- Type added added H₁₅/H₁₀ index (μ/100 H) tion Comp. 1 A 300 50.003 2.2 0.15 D Ex. Comp. 2 A 300 17.5 0.002 7.2 0.04 D Ex. Comp. 3 A300 32.5 0.003 13 0.04 CD Ex. Ex. 4 B 300 7.5 0.011 3.1 0.30 BC Ex. 5 B300 17.5 0.01 7.4 0.12 B Ex. 6 B 300 27.5 0.011 10.9 0.05 BC Comp. 7 C300 5 0.14 2.0 2.3 C Ex. Ex. 8 C 300 7.5 0.14 3.3 1.0 B Ex. 9 C 300 17.50.15 7.1 0.5 A Ex. 10 C 300 27.5 0.15 10.8 0.3 B Comp. 11 C 300 32.50.15 13.5 0.1 D Ex. Ex. 12 D 300 7.5 0.30 3.1 1.5 B Ex. 13 D 300 17.50.30 7.4 1.2 A Ex. 14 D 300 27.5 0.29 11.0 0.9 B Comp. 15 E 300 5 0.491.9 4.5 B Ex. Comp. 16 E 300 17.5 0.48 7.0 2.2 A Ex. Comp. 17 E 300 32.50.49 13.4 0.5 D Ex.

What is claimed is:
 1. A magnetic recording medium comprising anon-magnetic support, and a magnetic layer formed on the support andcomprising a binder resin and a ferromagnetic metal powder comprisingFe, said magnetic layer comprising an abrasive and a lubricant, theabrasive present on the surface of the magnetic layer satisfying therelationship below and the magnetic recording medium having a surfacelubricant index of 3 to 11; 0,01≦H₁₅/H₁₀≦0.3 wherein H₁₀ denotes thenumber of particles per unit area having a height less than 10 nm(particles/μm²) and H₁₅ denotes the number of particles per unit areahaving a height equal to or greater than 15 nm (particles/μm²).
 2. Themagnetic recording medium according to claim 1, wherein the abrasivepresent on the surface of the magnetic layer satisfying the relationshipbelow: 0,01≦H₁₅/H₁₀≦0.2
 3. The magnetic recording medium according toclaim 1, wherein the magnetic recording medium has a surface lubricantindex of 4 to
 11. 4. The magnetic recording medium according to claim 1,wherein the magnetic recording medium has been produced by a processwherein the abrasive is dispersed in a binder and a solvent in advanceto form a dispersion, the dispersion is then added to a magnetic liquidcontaining no abrasive to form a mixture, the mixture is then dispersedto give a magnetic coating solution, and the magnetic coating solutionis coated on the support.
 5. The magnetic recording medium according toclaim 1, wherein the magnetic recording medium has been subjected to acalendar treatment under ressure of 2,000 to 4,500 N/cm (200 to 450kg/cm), the processing temperature of 70° C. to 110° C. and theprocessing speed of 50 to 400 m/min.
 6. The magnetic recording mediumaccording to claim 1, wherein the magnetic recording medium has beensubjected to top-cutting the protrusions of the abrasive present on thesurface of the magnetic layer.
 7. The magnetic recording mediumaccording to claim 6, wherein the magnetic recording medium has beensubjected to a blade system involving lapping with an abrasive tape. 8.The magnetic recording medium according to claim 6, wherein the magneticrecording medium has been subjected to a blade system involving lappingwith a diamond powder-studded rotating roll.
 9. The magnetic recordingmedium according to claim 1, wherein an inoroganic non-magnetic powderis used as the abrasive.
 10. The magnetic recording medium according toclaim 9, wherein the inorganic non-magnetic powder is a metal oxide, ametal carbonate, a metal sulfate, a metal nitride, a metal carbide, or ametal sulfide.
 11. The magnetic recording medium according to claim 9,wherein the inorganic non-magnetic powder is α-alumina with anα-component proportion of 90% to 100%, ferric oxide, or chromium oxide.12. The magnetic recording medium according to claim 1, wherein anaverage particle size of the abrasive is 0.05 to 0.4 μm.
 13. Themagnetic recording medium according to claim 12, wherein abrasiveparticles with a particle size larger than the average particle size by0.1 μm or more are present at a proportion of 1 to 40%.
 14. The magneticrecording medium according to claim 1, wherein the ferromagnetic metalpowder has a specific surface area of 35 to 70 m²/g.
 15. The magneticrecording medium according to claim 1, wherein the ferromagnetic metalpowder has an oxide film on the surface.
 16. The magnetic recordingmedium according to claim 1, wherein the ferromagnetic powder comprisesat least one element selected from the group consisting of Al, Si, S,Ca, Ti, V, Cr, Cu, Mo, Rh, Pd, Ag, Sn, Sb, Te, Ba, Ta, W, Re, Au, Hg,Pb, Bi, P, Mn, Zn, Ni, Co, Sr, B, Y, La, Nd, Sm, and Gd.
 17. Themagnetic recording medium according to claim 1, wherein the lubricant amono-fatty acid ester formed from a monobasic fatty acid having 10 to 24carbons a monobasic fatty acid and a mono-, di-, tri-, tetra-, penta- orhexa-hydric alcohol having 12 to 22 carbons.
 18. The magnetic recordingmedium according to claim 1, wherein the lubricant is selected from thegroup consisting of lauric acid, myristic acid, palmitic acid, stearicacid, behenic acid, butyl stearate, oleic acid, linolic acid, linolenicacid, elaidic acid, octyl stearate, amyl stearate, isooctyl stearate,octyl myristate, and butoxyethyl stearate.